CA2003614C - Method for the manufacture of modified polypropylene compositions - Google Patents
Method for the manufacture of modified polypropylene compositionsInfo
- Publication number
- CA2003614C CA2003614C CA002003614A CA2003614A CA2003614C CA 2003614 C CA2003614 C CA 2003614C CA 002003614 A CA002003614 A CA 002003614A CA 2003614 A CA2003614 A CA 2003614A CA 2003614 C CA2003614 C CA 2003614C
- Authority
- CA
- Canada
- Prior art keywords
- polypropylene
- grafted
- aqueous solution
- weight
- treated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- -1 polypropylene Polymers 0.000 title claims abstract description 102
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 96
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 60
- 239000000203 mixture Substances 0.000 title abstract description 18
- 238000004519 manufacturing process Methods 0.000 title description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 87
- 239000007864 aqueous solution Substances 0.000 claims abstract description 37
- 238000010128 melt processing Methods 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 25
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 10
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims abstract description 7
- 229920000578 graft copolymer Polymers 0.000 claims description 34
- 150000001451 organic peroxides Chemical class 0.000 claims description 22
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 20
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 150000007513 acids Chemical class 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- 229920001519 homopolymer Polymers 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- 239000011976 maleic acid Substances 0.000 claims description 5
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims 2
- 150000001340 alkali metals Chemical class 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 2
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 claims 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 49
- 239000000243 solution Substances 0.000 abstract description 10
- 230000001070 adhesive effect Effects 0.000 abstract description 8
- 239000000853 adhesive Substances 0.000 abstract description 6
- 239000008188 pellet Substances 0.000 abstract description 5
- 238000009472 formulation Methods 0.000 abstract 1
- 239000000178 monomer Substances 0.000 description 25
- 239000000155 melt Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000001627 detrimental effect Effects 0.000 description 4
- 229920000297 Rayon Polymers 0.000 description 3
- 229920001112 grafted polyolefin Polymers 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 description 1
- MFGALGYVFGDXIX-UHFFFAOYSA-N 2,3-Dimethylmaleic anhydride Chemical compound CC1=C(C)C(=O)OC1=O MFGALGYVFGDXIX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- MSJMDZAOKORVFC-UAIGNFCESA-L disodium maleate Chemical compound [Na+].[Na+].[O-]C(=O)\C=C/C([O-])=O MSJMDZAOKORVFC-UAIGNFCESA-L 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 229920001198 elastomeric copolymer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 description 1
- 229940117927 ethylene oxide Drugs 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- VRVKOZSIJXBAJG-ODZAUARKSA-M sodium;(z)-but-2-enedioate;hydron Chemical compound [Na+].OC(=O)\C=C/C([O-])=O VRVKOZSIJXBAJG-ODZAUARKSA-M 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
A method for the treatment of melt-grafted polypropylene to improve adhesive properties thereof is disclosed. Molten grafted polypropylene, formed by melt grafting polypropylene with an alpha, beta unsaturated carboxylic acid or anhydride, is treated in melt processing apparatus with a minor amount of an aqueous solution of an alkaline material e.g. an aqueous solution of sodium hydroxide. The thus treated grafted polypropylene is separated from the agueous solution and recovered e.g. in the form of pellets. The melt-grafted polypropylene may be formed in the melt processing apparatus prior to treatment with the aqueous solution or polypropylene that has been grafted in a previous operation may be fed to the apparatus. The treated polymer may be used in adhesive formulations.
Description
2~03614 HETHOD FOR MANUFACTURE
OF MODIFIED POLYPROPYLENE COMPOSITIONS
The present invention relates to a method for the manufacture of modified polypropylene compositions, and especially to the grafting of alpha,beta unsaturated carboxylic acids and anhydrides on to polypropylene in a manner that results in improved adhesion of the polypropylene to polar materials.
Polypropylene is used in a wide variety of end-uses. However, it is a non-polar polymer and thus tends to exhibit poor or no adhesion to polar materials. A number of proposals have been made to improve the adhesive properties of polypropylene, including the grafting of alpha,beta unsaturated carboxylic acids and anhydrides onto the polypropylene backbone. For example, Japanese patent application No. 44-15422 of F. Ide et al, Mitsubishi Rayon Co., published (kokoku) on 1969 July 09, discloses the grafting of polypropylene in solution. Japanese patent application No. 53-18144 of K. Sadakata et al, Mitsubishi Rayon Co., published (kokoku) on 1968 August 01, discloses the grafting of polypropylene in a slurry state. Japanese patent application No.
43-27421 of F. Ide et al, Mitsubishi Rayon Co., published (kokoku) on 1968 November 26, discloses the grafting of polypropylene in a molten state.
The use of melt grafting techniques has the advantage of being a simple operation, and thus offers the potential of being the most economical method of grafting polypropylene. The grafting of molten propylene polymers is disclosed in U.K. patent 1 519 500 of BASF, published 1978 July 26. However, Japanese patent applications No. 57-65747 of Y. Wachi et al and No. 57-65746 of M. Fujiyama et al (Tokuyama Soda K.K.), both published 1982 April 21, disclose that the grafted polypropylene obtained from a melt grafting process contains residual unreacted monomer.
This residual monomer tends to cause lack of adhesion and the formation of blisters e.g. in moulding or other forming operations.
Methods for the removal of the residual monomer are known, including removal of the unreacted monomer using a solvent-precipitation technique and by agitation with a good solvent e. g. xylene, under conditions that do not dissolve the polymer, the latter being disclosed in Japanese patent application No. 54-99193 of Y. Nakajima et al, published 1979 August 04. European patent application 0 202 921 of T. Inoue et al, published 198~ November 26, which corresponds to U.S Patent 4 698 395, issued 1987 October 06, discloses treatment of grafted polyolefins by adding an aqueous solution of an alkali metal hydroxide to grafted polymer dissolved in organic solvent.
However, processes involving the use of solvent, often large amounts of solvent, add additional steps to the manufacture of grafted polypropylene including steps for the removal of the solvent from the grafted polymer until a commercially-acceptable low level of residual solvent is obtained in the polymer. The aforementioned application of Y. Wachi et al discloses two methods for the reduction in the amount of monomer viz.
heating the grafted composition to a temperature of 60~C or higher, and blending the grafted polymer with an ethylene/alpha-olefin copolymer and then heating the resultant mixture to a temperature of 60~C or higher. Compositions of grafted alpha-olefin polymer containing metal carbonates are disclosed in Japanese patent application No. 57 144 731 of Mitsui Polychemicals, published 1982 September 07. Addition of metal compounds e.g. calcium, magnesium or aluminum 2C03~1~
compounds, to grafted polyolefins is disclosed in Japanese patent application No. 57 080 046 of Toyo Ink Manufacturing KK, published 1982 May 20, and in Canadian Patent No. 1 009 787 of K.Shirayama et al, which issued 1977 May 03. Japanese patent application No. 56 118 411 of Mitsubishi Petrochemical KX, published 1981 September 17, discloses treatment of grafted polyolefin with hot water or hot air at a temperature between the softening point of the grafted polymer and a temperature 25~C lower than the softening point to improve the adhesion of the grafted polymer.
A method has now been found in which, in a melt grafting process, the component in grafted polypropylene that is believed to be detrimental to adhesion thereof to other materials may be removed and/or the effects thereof reduced.
Accordingly, the present invention provides a method for the treatment of melt-grafted polypropylene formed by the grafting of alpha,beta-unsaturated acids and anhydrides onto polypropylene, said method comprising the steps of:
(a) contacting molten grafted polypropylene in melt processing apparatus with a minor amount of an aqueous solution of an alkaline material, said melt-grafted polypropylene having been formed in melt processing apparatus by the grafting of polypropylene with 0.01 to 5% by weight of at least one of alpha,beta unsaturated carboxylic acids and alpha,beta-unsaturated carboxylic anhydrides and 0.01 to 2% byweight of an organic peroxide at a temperature above the melting point of the polypropylene;
(b) separating the thus treated grafted polypropylene from the aqueous solution; and (c) recovering grafted polypropylene.
2(~03614 The present invention further provides a method for the grafting of alpha,beta-unsaturated acids and anhydrides onto polypropylene comprising the steps of: -(a) admixing polypropylene in melt processing apparatus with 0.01 to 5% by weight of at least one of alpha,beta unsaturated carboxylic acids and alpha,beta-unsaturated carboxylic anhydrides and 0.01 to 2% by weight of an organic peroxide at a temperature above the melting point of the polypropylene;
(b) contacting the resultant molten grafted polypropylene in the melt processing apparatus with a minor amount of an aqueous solution of an alkaline material;
(c) separating the thus treated grafted polypropylene from the aqueous solution; and (d) recovering grafted polypropylene.
In a preferred embodiment of the process of the present invention, the polypropylene is grafted with maleic acid or, preferably, maleic anhydride.
In a further embodiment, the grafted polypropylene is treated with an aqueous solution of sodium hydroxide.
The component which has been believed to cause the detrimental effects in the adhesion of grafted polypropylene has been referred to above as residual monomer i.e. maleic anhydride, if the grafting monomer was maleic anhydride. While there may be evidence to that effect, there are also reasons to believe that detrimental effects are caused by low molecular weight polymers or adducts of maleic anhydride and propylene. It is known that propylene has a tendency to scission or de-polymerize in the presence of organic peroxides, thereby forming propylene monomer, and the propylene monomer may react with the grafting monomer e.g. maleic anhydride, to ~ 2()03614 form a low molecular weight copolymer or an adduct of propylene and maleic anhydride. However, the exact nature of the component that causes the detrimental effects in adhesion of grafted polypropylene to other materials is not critical to the present invention.
As used herein, the expression "polypropylene" refers to homopolymers of propylene, to impact or so-called block copolymers of propylene with ethylene in which the ethylene content is less than 25% by weight and to random copolymers of propylene with ethylene in which the ethylene content is less than 8% by weight. In preferred embodiments, the polypropylene is of relatively high molecular weight, especially polypropylene having a low melt flow index e.g. in the range of 0.5-1.5 dg/min, although the method of the present invention is not restricted to such polymers and may be used with polypropylenes having a broad range of molecular weights i.e. a broad range of melt flow indices.
The melt processing apparatus used in the method of the present invention preferably has a feed section, a section in which the grafted polymer may be contacted with a minor amount of the aqueous solution of alkaline material and a die or other device through which the grafted and treated polymer is discharged from the melt processing apparatus; if melt-grafted polypropylene is fed to the extruder, it is not necessary to have a section in the melt processing apparatus in which a grafting reaction may occur. The section in which the polymer is contacted with the aqueous solution would have an inlet port and an outlet port; the outlet port may be located upstream or downstream of the inlet port, or both. Melt processing apparatus having such ports is known, examples of which are extruders obtainable from Welding Engineers Inc. of Blue Bell, Pennsylvania, U.S.A., an embodiment of which is described in U.S.
Patent No. 3 742 093 of R.H. Skidmore, which issued 1973 June 26. Technigues for obt~;n;ng flow of solutions counter current to the extrusion of polymer in extruders is described in that patent. In preferred embodiments of the present invention, the melt proces~ing apparatus is a twin screw extruder that is equipped with non-intermeshing screws. The use of such apparatus in the grafting of monomers onto polypropylene is described in greater detail in European Patent No. 0 870 735 of E.C. Kelusky.
The melt processing apparatus is equipped with a mixing screw that is adapted to admix the components fed to the melt processing apparatus and to admix the grafted polymer with the aqueous solution of the alkaline material. It is most important, especially with respect to the uniformity of the product obtained by the method of the present invention, that a sufficiently high degree of mixing be achieved both during any grafting step and during the treatment step with alkaline material.
In the preferred method of the invention, polypropylene, grafting monomer and organic peroxide are fed to the melt processing apparatus. The polypropylene is as defined above, with homopolymer being preferred. The molecular weight of the polypropylene will depend on the intended end-use of the grafted polymer, it being understood that the molecular weight of the polypropylene will likely be decreased significantly during the grafting reaction, as will be understood by those skilled in the art.
The grafting monomer is at least one of alpha,beta-ethylenically unsaturated carboxylic acids and anhydrides, including derivatives of such acids and anhydrides, and including mixtures thereof.
Examples of the acids and anhydrides, which may be mono-, di- or polycarboxylic acids, are acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic 2(}0361~
acid, crotonic acid, itaconic anhydride, maleic anhydride and substituted maleic anhydride e.g.
dimethyl maleic anhydride. Examples of derivatives of the unsaturated acids are salts, amides, imides and 5 esters e.g. mono- and disodium maleate, acrylamide, maleimide and diethyl fumarate.
The amount of grafting monomer is in the range of 0.01 to 5% by weight of the polymer. In preferred embodiments, the amount of grafting monomer is in the range of 0.1 to 2%, especially 0.2 to 1.5%
and particularly 0.2 to 0.6%, by weight of the polymer. The grafting monomer may be fed directly to the melt processing apparatus or, alternatively, coated onto pellets or other comminuted shapes of a polymer or blended into polymer and fed to the melt processing apparatus. The polymer may be the polymer that is to be grafted or, preferably, is a polymer of higher melt index i.e. lower molecular weight, so as to facilitate admixing of polypropylene with the grafting monomer.
The organic peroxide, which as used herein includes hydroperoxides, may for example be a bis(tert. alkyl peroxy alkyl) benzene, dicumyl peroxide or acetylenic diperoxy compound. Other organic peroxides are known to those skilled in the art, including t-butyl hydroperoxide and di-t-butyl peroxide. The peroxides used in the method of the present invention preferably have a half-life at 150-C
of from about one minute to about 120 minutes. A
preferred organic peroxide is 2,5-dimethyl-2,5-bis-(tert. butyl peroxyisopropyl) benzene which is available under the trademark Vulcup from Hercules Inc. Other preferred organic peroxides are 2,5-dimethyl-2,5-di-(tert. butyl peroxy) hexane and 2,5-dimethyl-2,5-di-(tert. butyl peroxy) hexyne-3, which are available under the trademarks Lupersol 101 and Lupersol 130, respectively, from Lucidol Division of Pennwalt Corporation.
2()~)361*
The amount of organic peroxide is in the range of 0.01% to 1% by weight of the polymer, especially in the range 0.05 to 0.5% by weight of the polymer. However, as will be understood by those skilled in the art, the amount of organic peroxide may depend on the nature and amount of any additives in the polymer. For example, the polypropylene may contain stabilizing agents, especially antioxidants, although it is preferred that stabilizing agents be added subsequent to both the grafting reaction and the treatment step in the method of the present invention. The organic peroxide may be fed directly to the melt processing apparatus or, alternatively, coated onto pellets or other comminuted shapes of a polymer or blended into polymer and fed to the melt processing apparatus. The polymer may be the polymer that is to be grafted or, preferably, is a polymer of higher melt index i.e. lower molecular weight, so as to facilitate admixing of polypropyiene with the organic peroxide.
In embodiments, the polypropylene, grafting monomer and organic peroxide are admixed in the melt processing apparatus under conditions such that the polymer is in a molten state and which provide a degree of mixing of polymer, monomer and organic peroxide so that a grafted product of commercially acceptable uniformity is obtained. Such a degree of mixing will be understood by those skilled in the art. The temperature of the polymer will be above the melting point of the polymer; it will, however, be appreciated that chain scission of polypropylene tends to occur more readily at higher temperatures, which lowers the molecular weight of the polymer, and thus the temperature of the polymer is usually controlled above but relatively close to the melting point of the polymer. The organic peroxide will be selected so that the half-life of the peroxide under the melt - ~0~361~
g processing conditions is of a sufficient duration to obtain the uniform product. As will be appreciated, if the half-life is too short the uniformity of the grafting process will be affected, and if the half-life is too long the amount of organic peroxide that has not decomposed when the treatment step is reached will be at too high a level, to the detriment of the uniformity and quality of the product. For example, the period of time that the polypropylene is in a molten condition in the melt processing apparatus prior to reaching the treatment with alkaline material should be at least five times the half-life of the organic peroxide at the temperature of the polypropylene.
The grafted polypropylene, whether grafted in the melt processing apparatus or fed as such to the melt processing apparatus, is contacted with an aqueous solution of an alkaline material. The alkaline material is preferably an alkali metal hydroxide, carbonate and/or bicarbonate, of which sodium hydroxide is the preferred alkaline material.
The alkaline material must be capable of being dissolved or uniformly dispersed in a fine particle size in the aqueous solution, so that a high degree of mixing of polymer and alkaline material is obtainable in the melt processing apparatus.
In the method, the aqueous solution is fed to the inlet port of the melt processing apparatus and admixed with the grafted polymer in the melt processing apparatus. Preferably, a high degree of a~iYing of the aqueous solution and polymer is achieved, so that a high degree of contact between the alkaline material and the residual monomer, or other monomer by-products e.g. by-products formed in reactions with maleic acid or anhydride, is obtained prior to the aqueous solution passing from the melt processing apparatus through the outlet port. The 2(~)361~
.
amount of treatment achieved and hence the potential improvement in the adhesion obtainable with the grafted polypropylene will be related to the degree of admixing achieved between the grafted polymer and alkaline material. In an embodiment of the method of the invention, a 0.05-15% by weight, especially 0.1-10% by weight, aqueous solution of sodium hydroxide is fed to the melt processing apparatus such that the rate of flow of solution is 1-15%, especially 3-7%, by weight, of the rate of extrusion of the polymer through the melt processing apparatus.
Subsequent to the treatment of the grafted polymer with alkaline material, the treated polymer is discharged from the melt processing apparatus. For example, the treated polymer may be extruded through a die and converted to a suitable comminuted shape e.g.
pellets.
In embodiments of the method of the invention, additional polymers and/or stabilizing agents, pigments or the like are added to the grafted polymer subsequent to the treatment with alkaline material but prior to extrusion of the grafted polymer from the melt processing apparatus. For example, additional polypropylene may be added, especially to decrease the melt index of the grafted polymer composition. Toughening agents, for example, elastomers may be added e.g. in amounts of up to about 25% by weight of the composition, but any such toughening agents should be highly dispersed in the resultant composition. Furthermore, metal oxides or hydroxides e.g. calcium oxide, may be added, for example in amounts of up to 10% by weight, to further improve the adhesive characteristics of the resultant compositions.
As noted above, the method of treatment of the grafted material with alkaline material may be operated by feeding a grafted polypropylene to the 2()~)3614 ..
melt processing apparatus, rather than the mixture of polymer, monomer and organic peroxide. Thus the grafted polymer would be fed to the apparatus and, in a molten state, contacted with the alkaline material.
The grafted polypropylene that has been treated using the method of the present invention may be used in a variety of end-uses, including in adhesive compositions. For instance, the grafted polypropylene may be admixed with other polymers, examples of which are polyethylene, polypropylene, ethylene/vinyl acetate copolymers, ethylene/ethyl acrylate or methacrylate copolymers, ethylene/carbon monoxide/alkyl acrylate copolymers, elastomeric copolymers and the like, in order to form adhesive compositions.
The present invention is illustrated by the following examples:
Example I
The extruder used in this example was a 2.0 cm non-intermeshing, counter-rotating twin screw extruder. The extruder had a barrel with a ratio of length:diameter (L/D) of 60:1, and was equipped with vents ports at L/D positions (as measured from the inlet) of 33:1 and 45:1 and a liquid (solvent) injection port between the vents, at an L/D of 40:1.
The extruder was operated at 350 rpm and a barrel temperature of 170~C; the final melt temperature of the polymer was 210-C. The polymer was extruded from the extruder in the form of a strand, which was fed to a water bath and pelletized.
The following composition was fed to the inlet of the extruder:
(a) 100 parts by weight of powdered homopolymer polypropylene having a melt flow index of 0.6 dg/min, obtained from Himont Inc. under the trade designation PP6801;
- Z(~3614 (b) 0.3 parts by weight of Lupersol 101 organic peroxide, which was coated on the powdered polypropylene; and (c) 0.9 parts by weight of maleic anhydride, which was in the form of a crystalline powder and which was physically admixed with the coated polypropylene.
In Run 1, which was a comparative run, the composition was extruded, without injection of liquid to the extruder and with use of only atmospheric venting at the vent ports. The pelletized grafted polymer obtained was analyzed for graft content using infrared analysis and for residual maleic anhydride using high performance liquid chromatography.
The grafted polymer was tested for adhesion as follows:
A film (0.1 mm) of the grafted polymer, formed by pressing pellets between sheets of Teflon~
fluoropolymer, was placed between sheets of aluminum (0.2 mm) that had been pre-cleaned with carbon tetrachloride. The resultant sandwich was heated at 220~C for 10 minutes and then pressed (70 kg/cm2) for one minute at 220~C. The laminate obtained was cut into a number of strips measuring 200 x 25 mm, which were subjected to a 180~ peel test, at 23 C and 50% relative humidity, using an Instron* testing apparatus.
In Run 2, which was also a comparative run, the procedure of Run 1 was repeated, except that a vacuum of 100 mm Hg was applied to both of the vent ports.
In Run 3, which was a further comparative run, the procedure of Run 2 was repeated, except that water was injected through the injection port between the vent ports at a rate that was 4.5~ of the polymer extrusion rate.
* denotes trade mark )3614 In Run 4, which was a run of the invention, the procedure of Run 3 was repeated, except that an aqueous solution of sodium hydroxide (0.1% by weight) was injected at a rate that was 3.7~ of the polymer extrusion rate.
In Run 5, which was a run of the invention, the procedure of Run 4 was repeated except that the aqueous solution contained 1.0% by weight of sodium hydroxide.
In Run 6, which was a comparative run, the procedure of Run 4 was repeated except that the aqueous solution was replaced with acetone.
The adhesion results obtained are reported in Table I.
TABLE I
Run Vacuum Solvent Grafted Residual Adhesion No. (mm)Monomer Monomer (g/cm) (%)* (~)**
1 0 - 0.36 735 o 2 100 - 0.31 166 500 3 100 water 0.26 147 485 100 0.1% NaOH 0.29 263 555 5 100 1.0% NaOH 0.27 163 735 6 100 acetone 0.25 65 520 * obtained by infrared analysis ** obtained by liquid chromatography The results show that the application of a vacuum and contacting with a solution improves the adhesive characteristics of the resultant polymer.
The runs of the invention, Runs 4 and 5 in which the grafted polymer was washed with sodium hydroxide, gave the best results, especially Run 5 which used the higher concentration of sodium hydroxide.
2(~()3614 Example II
The extruder used in this example was a counter rotating, non-intermeshing twin screw extruder having a 2.0 cm screw and an L/D of 72:1. Vents were located in the extruder at L/D's of 51:1 and 63:1, and an injection port was located at 58:1. The temperature of the polymer was 170~C and the extruder was operated at 400 rpm.
The following polymer composition was fed to the extruder in the form of a mixture:
(a) 100 parts of impact-grade copolymer polypropylene powder having a melt flow index of 0.8 dg/min, obtained from Himont Inc. under the trade designation pp7701;
(b) 1 part of dicumyl peroxide (40% on clay); and (c) 1 part of crystalline maleic anhydride.
The polymer extruded from the extruder was subjected to the same procedure as in Example I.
In Run 7, which was a comparative run, a vacuum of 50 mm was applied at each vent port, but solution was not injected through the injection port.
In Run 8, which was a run of the invention, the procedure of Run 7 was repeated except that an aqueous solution of 0.5% by weight of sodium hydroxide was injected through the injection port at a rate of 5% by weight of the polymer flow.
In Run 9, which was a run of the invention, the procedure of Run 8 was repeated except that the solution was 2.5% by weight of sodium hydroxide.
20~)3~
The results obtained are given in Table II.
TABLE II
Run Vacuum Solvent Grafted Residual Adhesion 5 No. (mm) Honomer Monomer (g/cm) (%) (%) 7 50 - 0.37 658 <180 8 50 0.5% NaOH 0.27 88 355 9 50 2.5% NaOH 0.27 44 625 The results show that treating with sodium hydroxide improved the adhesive characteristics of the grafted polymer, especially when the higher level of sodium hydroxide was used.
In another peel test, a 0.073 mm thick sample of grafted polymer was pressed to a pre-cleaned aluminum sheet using a heat sealer, at 210~C and a pressure of 3.6 kg/cm2 for 5 seconds.
The peel strengths obtained were as follows: for the grafted polymer of Run 7, O g/cm; for the grafted polymer of Run 8, 445 g/cm; and for the grafted polymer of Run 9, >895 g/cm which was the yield strength of the sample of polymer. This test also illustrates the improvement obtained with the present invention.
Example III
A homopolymer of propylene was grafted with maleic anhydride, in the presence of an organic peroxide catalyst, in a Berstorff* twin screw extruder. The product obtained contained 0.1% by weight of grafted maleic anhydride and had a melt flow index of 10 dg/min.
The grafted polymer was fed to a 5.0 cm counter rotating non-intermeshing twin screw extruder where it was melted and then washed with an aqueous * denotes trade mark 2C~)3~14 . ~ .
solution of sodium hydroxide using the procedure described in Example I. The grafted and treated polymers were tested for adhesion using the procedure described in Example I. Run 10 is a comparative run, using the grafted polymer prepared on the Berstorff extruder; in Runs 11 to 14, which are runs of the invention, the grafted polymer was subjected to washing with aqueous sodium hydroxide solution as indicated.
Further details and the results obtained are given in Table III.
TABLE III
15 Run Vacuum SolventAdhesion No. (mm) (g/cm) -- -- 0*
11 50 2.5% NaOH 2680 12 50 5.0% NaOH 1910 13 50 7.5% NaOH 2070 14 50 10.0% NaOH2790 * without treatment with sodium hydroxide solution The results show that a grafted polymer viz.
grafted polypropylene may be formed without being treated as disclosed herein and subsequently treated with the aqueous solution of sodium hydroxide while in the molten condition, according to the method of the present invention, to provide a grafted polymer with good adhesion properties. In this example, treatment of the grafted polymer with water instead of with the alkaline solution resulted in no adhesion in the adhesion test.
20~3614 The grafted polymer was also washed with acetone but in an adhesion test in which the molten grafted polymer was pressed to aluminum and the adhesion tested by hand, the adhesion obtained was poor.
OF MODIFIED POLYPROPYLENE COMPOSITIONS
The present invention relates to a method for the manufacture of modified polypropylene compositions, and especially to the grafting of alpha,beta unsaturated carboxylic acids and anhydrides on to polypropylene in a manner that results in improved adhesion of the polypropylene to polar materials.
Polypropylene is used in a wide variety of end-uses. However, it is a non-polar polymer and thus tends to exhibit poor or no adhesion to polar materials. A number of proposals have been made to improve the adhesive properties of polypropylene, including the grafting of alpha,beta unsaturated carboxylic acids and anhydrides onto the polypropylene backbone. For example, Japanese patent application No. 44-15422 of F. Ide et al, Mitsubishi Rayon Co., published (kokoku) on 1969 July 09, discloses the grafting of polypropylene in solution. Japanese patent application No. 53-18144 of K. Sadakata et al, Mitsubishi Rayon Co., published (kokoku) on 1968 August 01, discloses the grafting of polypropylene in a slurry state. Japanese patent application No.
43-27421 of F. Ide et al, Mitsubishi Rayon Co., published (kokoku) on 1968 November 26, discloses the grafting of polypropylene in a molten state.
The use of melt grafting techniques has the advantage of being a simple operation, and thus offers the potential of being the most economical method of grafting polypropylene. The grafting of molten propylene polymers is disclosed in U.K. patent 1 519 500 of BASF, published 1978 July 26. However, Japanese patent applications No. 57-65747 of Y. Wachi et al and No. 57-65746 of M. Fujiyama et al (Tokuyama Soda K.K.), both published 1982 April 21, disclose that the grafted polypropylene obtained from a melt grafting process contains residual unreacted monomer.
This residual monomer tends to cause lack of adhesion and the formation of blisters e.g. in moulding or other forming operations.
Methods for the removal of the residual monomer are known, including removal of the unreacted monomer using a solvent-precipitation technique and by agitation with a good solvent e. g. xylene, under conditions that do not dissolve the polymer, the latter being disclosed in Japanese patent application No. 54-99193 of Y. Nakajima et al, published 1979 August 04. European patent application 0 202 921 of T. Inoue et al, published 198~ November 26, which corresponds to U.S Patent 4 698 395, issued 1987 October 06, discloses treatment of grafted polyolefins by adding an aqueous solution of an alkali metal hydroxide to grafted polymer dissolved in organic solvent.
However, processes involving the use of solvent, often large amounts of solvent, add additional steps to the manufacture of grafted polypropylene including steps for the removal of the solvent from the grafted polymer until a commercially-acceptable low level of residual solvent is obtained in the polymer. The aforementioned application of Y. Wachi et al discloses two methods for the reduction in the amount of monomer viz.
heating the grafted composition to a temperature of 60~C or higher, and blending the grafted polymer with an ethylene/alpha-olefin copolymer and then heating the resultant mixture to a temperature of 60~C or higher. Compositions of grafted alpha-olefin polymer containing metal carbonates are disclosed in Japanese patent application No. 57 144 731 of Mitsui Polychemicals, published 1982 September 07. Addition of metal compounds e.g. calcium, magnesium or aluminum 2C03~1~
compounds, to grafted polyolefins is disclosed in Japanese patent application No. 57 080 046 of Toyo Ink Manufacturing KK, published 1982 May 20, and in Canadian Patent No. 1 009 787 of K.Shirayama et al, which issued 1977 May 03. Japanese patent application No. 56 118 411 of Mitsubishi Petrochemical KX, published 1981 September 17, discloses treatment of grafted polyolefin with hot water or hot air at a temperature between the softening point of the grafted polymer and a temperature 25~C lower than the softening point to improve the adhesion of the grafted polymer.
A method has now been found in which, in a melt grafting process, the component in grafted polypropylene that is believed to be detrimental to adhesion thereof to other materials may be removed and/or the effects thereof reduced.
Accordingly, the present invention provides a method for the treatment of melt-grafted polypropylene formed by the grafting of alpha,beta-unsaturated acids and anhydrides onto polypropylene, said method comprising the steps of:
(a) contacting molten grafted polypropylene in melt processing apparatus with a minor amount of an aqueous solution of an alkaline material, said melt-grafted polypropylene having been formed in melt processing apparatus by the grafting of polypropylene with 0.01 to 5% by weight of at least one of alpha,beta unsaturated carboxylic acids and alpha,beta-unsaturated carboxylic anhydrides and 0.01 to 2% byweight of an organic peroxide at a temperature above the melting point of the polypropylene;
(b) separating the thus treated grafted polypropylene from the aqueous solution; and (c) recovering grafted polypropylene.
2(~03614 The present invention further provides a method for the grafting of alpha,beta-unsaturated acids and anhydrides onto polypropylene comprising the steps of: -(a) admixing polypropylene in melt processing apparatus with 0.01 to 5% by weight of at least one of alpha,beta unsaturated carboxylic acids and alpha,beta-unsaturated carboxylic anhydrides and 0.01 to 2% by weight of an organic peroxide at a temperature above the melting point of the polypropylene;
(b) contacting the resultant molten grafted polypropylene in the melt processing apparatus with a minor amount of an aqueous solution of an alkaline material;
(c) separating the thus treated grafted polypropylene from the aqueous solution; and (d) recovering grafted polypropylene.
In a preferred embodiment of the process of the present invention, the polypropylene is grafted with maleic acid or, preferably, maleic anhydride.
In a further embodiment, the grafted polypropylene is treated with an aqueous solution of sodium hydroxide.
The component which has been believed to cause the detrimental effects in the adhesion of grafted polypropylene has been referred to above as residual monomer i.e. maleic anhydride, if the grafting monomer was maleic anhydride. While there may be evidence to that effect, there are also reasons to believe that detrimental effects are caused by low molecular weight polymers or adducts of maleic anhydride and propylene. It is known that propylene has a tendency to scission or de-polymerize in the presence of organic peroxides, thereby forming propylene monomer, and the propylene monomer may react with the grafting monomer e.g. maleic anhydride, to ~ 2()03614 form a low molecular weight copolymer or an adduct of propylene and maleic anhydride. However, the exact nature of the component that causes the detrimental effects in adhesion of grafted polypropylene to other materials is not critical to the present invention.
As used herein, the expression "polypropylene" refers to homopolymers of propylene, to impact or so-called block copolymers of propylene with ethylene in which the ethylene content is less than 25% by weight and to random copolymers of propylene with ethylene in which the ethylene content is less than 8% by weight. In preferred embodiments, the polypropylene is of relatively high molecular weight, especially polypropylene having a low melt flow index e.g. in the range of 0.5-1.5 dg/min, although the method of the present invention is not restricted to such polymers and may be used with polypropylenes having a broad range of molecular weights i.e. a broad range of melt flow indices.
The melt processing apparatus used in the method of the present invention preferably has a feed section, a section in which the grafted polymer may be contacted with a minor amount of the aqueous solution of alkaline material and a die or other device through which the grafted and treated polymer is discharged from the melt processing apparatus; if melt-grafted polypropylene is fed to the extruder, it is not necessary to have a section in the melt processing apparatus in which a grafting reaction may occur. The section in which the polymer is contacted with the aqueous solution would have an inlet port and an outlet port; the outlet port may be located upstream or downstream of the inlet port, or both. Melt processing apparatus having such ports is known, examples of which are extruders obtainable from Welding Engineers Inc. of Blue Bell, Pennsylvania, U.S.A., an embodiment of which is described in U.S.
Patent No. 3 742 093 of R.H. Skidmore, which issued 1973 June 26. Technigues for obt~;n;ng flow of solutions counter current to the extrusion of polymer in extruders is described in that patent. In preferred embodiments of the present invention, the melt proces~ing apparatus is a twin screw extruder that is equipped with non-intermeshing screws. The use of such apparatus in the grafting of monomers onto polypropylene is described in greater detail in European Patent No. 0 870 735 of E.C. Kelusky.
The melt processing apparatus is equipped with a mixing screw that is adapted to admix the components fed to the melt processing apparatus and to admix the grafted polymer with the aqueous solution of the alkaline material. It is most important, especially with respect to the uniformity of the product obtained by the method of the present invention, that a sufficiently high degree of mixing be achieved both during any grafting step and during the treatment step with alkaline material.
In the preferred method of the invention, polypropylene, grafting monomer and organic peroxide are fed to the melt processing apparatus. The polypropylene is as defined above, with homopolymer being preferred. The molecular weight of the polypropylene will depend on the intended end-use of the grafted polymer, it being understood that the molecular weight of the polypropylene will likely be decreased significantly during the grafting reaction, as will be understood by those skilled in the art.
The grafting monomer is at least one of alpha,beta-ethylenically unsaturated carboxylic acids and anhydrides, including derivatives of such acids and anhydrides, and including mixtures thereof.
Examples of the acids and anhydrides, which may be mono-, di- or polycarboxylic acids, are acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic 2(}0361~
acid, crotonic acid, itaconic anhydride, maleic anhydride and substituted maleic anhydride e.g.
dimethyl maleic anhydride. Examples of derivatives of the unsaturated acids are salts, amides, imides and 5 esters e.g. mono- and disodium maleate, acrylamide, maleimide and diethyl fumarate.
The amount of grafting monomer is in the range of 0.01 to 5% by weight of the polymer. In preferred embodiments, the amount of grafting monomer is in the range of 0.1 to 2%, especially 0.2 to 1.5%
and particularly 0.2 to 0.6%, by weight of the polymer. The grafting monomer may be fed directly to the melt processing apparatus or, alternatively, coated onto pellets or other comminuted shapes of a polymer or blended into polymer and fed to the melt processing apparatus. The polymer may be the polymer that is to be grafted or, preferably, is a polymer of higher melt index i.e. lower molecular weight, so as to facilitate admixing of polypropylene with the grafting monomer.
The organic peroxide, which as used herein includes hydroperoxides, may for example be a bis(tert. alkyl peroxy alkyl) benzene, dicumyl peroxide or acetylenic diperoxy compound. Other organic peroxides are known to those skilled in the art, including t-butyl hydroperoxide and di-t-butyl peroxide. The peroxides used in the method of the present invention preferably have a half-life at 150-C
of from about one minute to about 120 minutes. A
preferred organic peroxide is 2,5-dimethyl-2,5-bis-(tert. butyl peroxyisopropyl) benzene which is available under the trademark Vulcup from Hercules Inc. Other preferred organic peroxides are 2,5-dimethyl-2,5-di-(tert. butyl peroxy) hexane and 2,5-dimethyl-2,5-di-(tert. butyl peroxy) hexyne-3, which are available under the trademarks Lupersol 101 and Lupersol 130, respectively, from Lucidol Division of Pennwalt Corporation.
2()~)361*
The amount of organic peroxide is in the range of 0.01% to 1% by weight of the polymer, especially in the range 0.05 to 0.5% by weight of the polymer. However, as will be understood by those skilled in the art, the amount of organic peroxide may depend on the nature and amount of any additives in the polymer. For example, the polypropylene may contain stabilizing agents, especially antioxidants, although it is preferred that stabilizing agents be added subsequent to both the grafting reaction and the treatment step in the method of the present invention. The organic peroxide may be fed directly to the melt processing apparatus or, alternatively, coated onto pellets or other comminuted shapes of a polymer or blended into polymer and fed to the melt processing apparatus. The polymer may be the polymer that is to be grafted or, preferably, is a polymer of higher melt index i.e. lower molecular weight, so as to facilitate admixing of polypropyiene with the organic peroxide.
In embodiments, the polypropylene, grafting monomer and organic peroxide are admixed in the melt processing apparatus under conditions such that the polymer is in a molten state and which provide a degree of mixing of polymer, monomer and organic peroxide so that a grafted product of commercially acceptable uniformity is obtained. Such a degree of mixing will be understood by those skilled in the art. The temperature of the polymer will be above the melting point of the polymer; it will, however, be appreciated that chain scission of polypropylene tends to occur more readily at higher temperatures, which lowers the molecular weight of the polymer, and thus the temperature of the polymer is usually controlled above but relatively close to the melting point of the polymer. The organic peroxide will be selected so that the half-life of the peroxide under the melt - ~0~361~
g processing conditions is of a sufficient duration to obtain the uniform product. As will be appreciated, if the half-life is too short the uniformity of the grafting process will be affected, and if the half-life is too long the amount of organic peroxide that has not decomposed when the treatment step is reached will be at too high a level, to the detriment of the uniformity and quality of the product. For example, the period of time that the polypropylene is in a molten condition in the melt processing apparatus prior to reaching the treatment with alkaline material should be at least five times the half-life of the organic peroxide at the temperature of the polypropylene.
The grafted polypropylene, whether grafted in the melt processing apparatus or fed as such to the melt processing apparatus, is contacted with an aqueous solution of an alkaline material. The alkaline material is preferably an alkali metal hydroxide, carbonate and/or bicarbonate, of which sodium hydroxide is the preferred alkaline material.
The alkaline material must be capable of being dissolved or uniformly dispersed in a fine particle size in the aqueous solution, so that a high degree of mixing of polymer and alkaline material is obtainable in the melt processing apparatus.
In the method, the aqueous solution is fed to the inlet port of the melt processing apparatus and admixed with the grafted polymer in the melt processing apparatus. Preferably, a high degree of a~iYing of the aqueous solution and polymer is achieved, so that a high degree of contact between the alkaline material and the residual monomer, or other monomer by-products e.g. by-products formed in reactions with maleic acid or anhydride, is obtained prior to the aqueous solution passing from the melt processing apparatus through the outlet port. The 2(~)361~
.
amount of treatment achieved and hence the potential improvement in the adhesion obtainable with the grafted polypropylene will be related to the degree of admixing achieved between the grafted polymer and alkaline material. In an embodiment of the method of the invention, a 0.05-15% by weight, especially 0.1-10% by weight, aqueous solution of sodium hydroxide is fed to the melt processing apparatus such that the rate of flow of solution is 1-15%, especially 3-7%, by weight, of the rate of extrusion of the polymer through the melt processing apparatus.
Subsequent to the treatment of the grafted polymer with alkaline material, the treated polymer is discharged from the melt processing apparatus. For example, the treated polymer may be extruded through a die and converted to a suitable comminuted shape e.g.
pellets.
In embodiments of the method of the invention, additional polymers and/or stabilizing agents, pigments or the like are added to the grafted polymer subsequent to the treatment with alkaline material but prior to extrusion of the grafted polymer from the melt processing apparatus. For example, additional polypropylene may be added, especially to decrease the melt index of the grafted polymer composition. Toughening agents, for example, elastomers may be added e.g. in amounts of up to about 25% by weight of the composition, but any such toughening agents should be highly dispersed in the resultant composition. Furthermore, metal oxides or hydroxides e.g. calcium oxide, may be added, for example in amounts of up to 10% by weight, to further improve the adhesive characteristics of the resultant compositions.
As noted above, the method of treatment of the grafted material with alkaline material may be operated by feeding a grafted polypropylene to the 2()~)3614 ..
melt processing apparatus, rather than the mixture of polymer, monomer and organic peroxide. Thus the grafted polymer would be fed to the apparatus and, in a molten state, contacted with the alkaline material.
The grafted polypropylene that has been treated using the method of the present invention may be used in a variety of end-uses, including in adhesive compositions. For instance, the grafted polypropylene may be admixed with other polymers, examples of which are polyethylene, polypropylene, ethylene/vinyl acetate copolymers, ethylene/ethyl acrylate or methacrylate copolymers, ethylene/carbon monoxide/alkyl acrylate copolymers, elastomeric copolymers and the like, in order to form adhesive compositions.
The present invention is illustrated by the following examples:
Example I
The extruder used in this example was a 2.0 cm non-intermeshing, counter-rotating twin screw extruder. The extruder had a barrel with a ratio of length:diameter (L/D) of 60:1, and was equipped with vents ports at L/D positions (as measured from the inlet) of 33:1 and 45:1 and a liquid (solvent) injection port between the vents, at an L/D of 40:1.
The extruder was operated at 350 rpm and a barrel temperature of 170~C; the final melt temperature of the polymer was 210-C. The polymer was extruded from the extruder in the form of a strand, which was fed to a water bath and pelletized.
The following composition was fed to the inlet of the extruder:
(a) 100 parts by weight of powdered homopolymer polypropylene having a melt flow index of 0.6 dg/min, obtained from Himont Inc. under the trade designation PP6801;
- Z(~3614 (b) 0.3 parts by weight of Lupersol 101 organic peroxide, which was coated on the powdered polypropylene; and (c) 0.9 parts by weight of maleic anhydride, which was in the form of a crystalline powder and which was physically admixed with the coated polypropylene.
In Run 1, which was a comparative run, the composition was extruded, without injection of liquid to the extruder and with use of only atmospheric venting at the vent ports. The pelletized grafted polymer obtained was analyzed for graft content using infrared analysis and for residual maleic anhydride using high performance liquid chromatography.
The grafted polymer was tested for adhesion as follows:
A film (0.1 mm) of the grafted polymer, formed by pressing pellets between sheets of Teflon~
fluoropolymer, was placed between sheets of aluminum (0.2 mm) that had been pre-cleaned with carbon tetrachloride. The resultant sandwich was heated at 220~C for 10 minutes and then pressed (70 kg/cm2) for one minute at 220~C. The laminate obtained was cut into a number of strips measuring 200 x 25 mm, which were subjected to a 180~ peel test, at 23 C and 50% relative humidity, using an Instron* testing apparatus.
In Run 2, which was also a comparative run, the procedure of Run 1 was repeated, except that a vacuum of 100 mm Hg was applied to both of the vent ports.
In Run 3, which was a further comparative run, the procedure of Run 2 was repeated, except that water was injected through the injection port between the vent ports at a rate that was 4.5~ of the polymer extrusion rate.
* denotes trade mark )3614 In Run 4, which was a run of the invention, the procedure of Run 3 was repeated, except that an aqueous solution of sodium hydroxide (0.1% by weight) was injected at a rate that was 3.7~ of the polymer extrusion rate.
In Run 5, which was a run of the invention, the procedure of Run 4 was repeated except that the aqueous solution contained 1.0% by weight of sodium hydroxide.
In Run 6, which was a comparative run, the procedure of Run 4 was repeated except that the aqueous solution was replaced with acetone.
The adhesion results obtained are reported in Table I.
TABLE I
Run Vacuum Solvent Grafted Residual Adhesion No. (mm)Monomer Monomer (g/cm) (%)* (~)**
1 0 - 0.36 735 o 2 100 - 0.31 166 500 3 100 water 0.26 147 485 100 0.1% NaOH 0.29 263 555 5 100 1.0% NaOH 0.27 163 735 6 100 acetone 0.25 65 520 * obtained by infrared analysis ** obtained by liquid chromatography The results show that the application of a vacuum and contacting with a solution improves the adhesive characteristics of the resultant polymer.
The runs of the invention, Runs 4 and 5 in which the grafted polymer was washed with sodium hydroxide, gave the best results, especially Run 5 which used the higher concentration of sodium hydroxide.
2(~()3614 Example II
The extruder used in this example was a counter rotating, non-intermeshing twin screw extruder having a 2.0 cm screw and an L/D of 72:1. Vents were located in the extruder at L/D's of 51:1 and 63:1, and an injection port was located at 58:1. The temperature of the polymer was 170~C and the extruder was operated at 400 rpm.
The following polymer composition was fed to the extruder in the form of a mixture:
(a) 100 parts of impact-grade copolymer polypropylene powder having a melt flow index of 0.8 dg/min, obtained from Himont Inc. under the trade designation pp7701;
(b) 1 part of dicumyl peroxide (40% on clay); and (c) 1 part of crystalline maleic anhydride.
The polymer extruded from the extruder was subjected to the same procedure as in Example I.
In Run 7, which was a comparative run, a vacuum of 50 mm was applied at each vent port, but solution was not injected through the injection port.
In Run 8, which was a run of the invention, the procedure of Run 7 was repeated except that an aqueous solution of 0.5% by weight of sodium hydroxide was injected through the injection port at a rate of 5% by weight of the polymer flow.
In Run 9, which was a run of the invention, the procedure of Run 8 was repeated except that the solution was 2.5% by weight of sodium hydroxide.
20~)3~
The results obtained are given in Table II.
TABLE II
Run Vacuum Solvent Grafted Residual Adhesion 5 No. (mm) Honomer Monomer (g/cm) (%) (%) 7 50 - 0.37 658 <180 8 50 0.5% NaOH 0.27 88 355 9 50 2.5% NaOH 0.27 44 625 The results show that treating with sodium hydroxide improved the adhesive characteristics of the grafted polymer, especially when the higher level of sodium hydroxide was used.
In another peel test, a 0.073 mm thick sample of grafted polymer was pressed to a pre-cleaned aluminum sheet using a heat sealer, at 210~C and a pressure of 3.6 kg/cm2 for 5 seconds.
The peel strengths obtained were as follows: for the grafted polymer of Run 7, O g/cm; for the grafted polymer of Run 8, 445 g/cm; and for the grafted polymer of Run 9, >895 g/cm which was the yield strength of the sample of polymer. This test also illustrates the improvement obtained with the present invention.
Example III
A homopolymer of propylene was grafted with maleic anhydride, in the presence of an organic peroxide catalyst, in a Berstorff* twin screw extruder. The product obtained contained 0.1% by weight of grafted maleic anhydride and had a melt flow index of 10 dg/min.
The grafted polymer was fed to a 5.0 cm counter rotating non-intermeshing twin screw extruder where it was melted and then washed with an aqueous * denotes trade mark 2C~)3~14 . ~ .
solution of sodium hydroxide using the procedure described in Example I. The grafted and treated polymers were tested for adhesion using the procedure described in Example I. Run 10 is a comparative run, using the grafted polymer prepared on the Berstorff extruder; in Runs 11 to 14, which are runs of the invention, the grafted polymer was subjected to washing with aqueous sodium hydroxide solution as indicated.
Further details and the results obtained are given in Table III.
TABLE III
15 Run Vacuum SolventAdhesion No. (mm) (g/cm) -- -- 0*
11 50 2.5% NaOH 2680 12 50 5.0% NaOH 1910 13 50 7.5% NaOH 2070 14 50 10.0% NaOH2790 * without treatment with sodium hydroxide solution The results show that a grafted polymer viz.
grafted polypropylene may be formed without being treated as disclosed herein and subsequently treated with the aqueous solution of sodium hydroxide while in the molten condition, according to the method of the present invention, to provide a grafted polymer with good adhesion properties. In this example, treatment of the grafted polymer with water instead of with the alkaline solution resulted in no adhesion in the adhesion test.
20~3614 The grafted polymer was also washed with acetone but in an adhesion test in which the molten grafted polymer was pressed to aluminum and the adhesion tested by hand, the adhesion obtained was poor.
Claims (20)
1. A method for the treatment of melt-grafted polypropylene formed by the grafting of alpha, beta-unsaturated acids and anhydrides onto polypropylene, said method comprising the steps of:
(a) contacting molten grafted polypropylene in melt processing apparatus with a minor amount of an aqueous solution of an alkaline material, said melt-grafted polypropylene having been formed in melt processing apparatus by the grafting of polypropylene with 0.01 to 5% by weight of at least one of alpha, beta unsaturated carboxylic acids and alpha, beta-unsaturated carboxylic anhydrides and 0.01 to 2% by weight of an organic peroxide at a temperature above the melting point of the polypropylene;
(b) separating the thus treated grafted polypropylene from the aqueous solution; and (c) recovering grafted polypropylene.
(a) contacting molten grafted polypropylene in melt processing apparatus with a minor amount of an aqueous solution of an alkaline material, said melt-grafted polypropylene having been formed in melt processing apparatus by the grafting of polypropylene with 0.01 to 5% by weight of at least one of alpha, beta unsaturated carboxylic acids and alpha, beta-unsaturated carboxylic anhydrides and 0.01 to 2% by weight of an organic peroxide at a temperature above the melting point of the polypropylene;
(b) separating the thus treated grafted polypropylene from the aqueous solution; and (c) recovering grafted polypropylene.
2. The method of Claim 1 in which the grafted polypropylene is treated with an aqueous solution of at least one of a hydroxide, carbonate and bicarbonate of an alkali metal.
3. The method of Claim 2 in which the grafted polypropylene is treated with an aqueous solution of sodium hydroxide.
4. The method of Claim 3 in which the grafted polypropylene is treated with an aqueous solution of 0.05-15% by weight of sodium hydroxide.
5. The method of Claim 3 in which the grafted polypropylene is treated with an aqueous solution of 0.1-10% by weight of sodium hydroxide.
6. The method of Claim 2 in which the polypropylene is grafted with at least one of maleic acid and maleic anhydride.
7. The method of Claim 6 in which the polypropylene is grafted with maleic anhydride and the amount of maleic anhydride is in the range of 0.1 to 0.4% by weight.
8. A method for the grafting of alpha, beta-unsaturated acids and anhydrides onto polypropylene comprising the steps of:
(a) admixing polypropylene in melt processing apparatus with 0.01 to 5% by weight of at least one of alpha, beta unsaturated carboxylic acids and alpha, beta-unsaturated carboxylic anhydrides and 0.01 to 2% by weight of an organic peroxide at a temperature above the melting point of the polypropylene;
(b) contacting the resultant molten grafted polypropylene in melt processing apparatus with a minor amount of an aqueous solution of an alkaline material;
(c) separating the thus treated grafted polypropylene from the aqueous solution; and (d) recovering grafted polypropylene.
(a) admixing polypropylene in melt processing apparatus with 0.01 to 5% by weight of at least one of alpha, beta unsaturated carboxylic acids and alpha, beta-unsaturated carboxylic anhydrides and 0.01 to 2% by weight of an organic peroxide at a temperature above the melting point of the polypropylene;
(b) contacting the resultant molten grafted polypropylene in melt processing apparatus with a minor amount of an aqueous solution of an alkaline material;
(c) separating the thus treated grafted polypropylene from the aqueous solution; and (d) recovering grafted polypropylene.
9. The method of Claim 7 in which the grafted polypropylene is treated with an aqueous solution of at least one of a hydroxide, carbonate and bicarbonate of an alkali metal.
10. The method of Claim 9 in which the grafted polypropylene is treated with an aqueous solution of sodium hydroxide.
11. The method of Claim 10 in which the grafted polypropylene is treated with an aqueous solution of 0.05-15% by weight of sodium hydroxide.
12. The method of Claim 10 in which the grafted polypropylene is treated with an aqueous solution of 0.1-10% by weight of sodium hydroxide.
13. The method of Claim 9 in which the polypropylene is grafted with at least one of maleic acid and maleic anhydride.
14. The method of Claim 13 in which the polypropylene is grafted with maleic anhydride and the amount of maleic anhydride is in the range of 0.1 to 0.4% by weight.
15. The method of any one of Claims 1-14 in which the amount of organic peroxide is in the range of 0.05 to 0.5% by weight.
16. The method of any one of Claims 1-14 in which the rate at which the aqueous solution is contacted with the grafted polypropylene is 1-15%, by weight, of the rate of extrusion of the grafted polymer.
17. The method of any one of Claims 1-14 in which the rate at which the aqueous solution is contacted with the grafted polypropylene is 3-7%, by weight, of the rate of extrusion of the grafted polymer.
18. The method of any one of Claims 1-14 in which the melt processing apparatus is a twin screw extruder with non-intermeshing counter rotating screws.
19. The method of any one of Claims 1-14 in which the polypropylene is a homopolymer of propylene.
20. The method of any one of Claims 1-14 in which the polypropylene is selected from the group consisting of block copolymers of ethylene and propylene containing less than 25% by weight of eithylene and random copolymers of ethylene and propylene containing less than 8% by weight of ethylene.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB888827335A GB8827335D0 (en) | 1988-11-23 | 1988-11-23 | Method for manufacture of modified polypropylene compositions |
GB88.27335 | 1988-11-23 |
Publications (2)
Publication Number | Publication Date |
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CA2003614A1 CA2003614A1 (en) | 1990-05-23 |
CA2003614C true CA2003614C (en) | 1999-07-13 |
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CA002003614A Expired - Fee Related CA2003614C (en) | 1988-11-23 | 1989-11-22 | Method for the manufacture of modified polypropylene compositions |
Country Status (5)
Country | Link |
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US (1) | US5137975A (en) |
EP (1) | EP0370736B1 (en) |
CA (1) | CA2003614C (en) |
DE (1) | DE68907320T2 (en) |
GB (1) | GB8827335D0 (en) |
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US5439974A (en) * | 1991-11-27 | 1995-08-08 | Quantum Chemical Corporation | Propylene-based extrudable adhesive blends |
US5367022A (en) * | 1991-11-27 | 1994-11-22 | Quantum Chemical Corporation | Grafted polymeric products, and adhesive blends |
US5319030A (en) * | 1992-07-23 | 1994-06-07 | Chevron Research And Technology Company | One-step process for the preparation of alkenyl succinic anhydride |
US5344888A (en) * | 1993-05-14 | 1994-09-06 | Quantum Chemical Corporation | Process for making graft propylene polymers |
US5344886A (en) * | 1993-05-14 | 1994-09-06 | Quantum Chemical Corporation | Process for making graft propylene polymers |
US5728776A (en) * | 1993-07-29 | 1998-03-17 | Kawasaki Steel Corporation | Process for producing graft modified polyolefins |
US5643989A (en) * | 1993-10-29 | 1997-07-01 | Azdel, Inc. | Fiber reinforced functionalized polyolefin composites |
US6187870B1 (en) * | 1993-12-16 | 2001-02-13 | Eastman Chemical Company | Apparatus and process for the production of low molecular weight grafted polyolefins |
BE1007888A3 (en) * | 1993-12-27 | 1995-11-14 | Solvay | Continuous process of polyolefin graft the grafted polyolefin obtained through this process. |
DE69612901T2 (en) * | 1995-03-27 | 2001-09-20 | Mitsubishi Chemical Corp., Tokio/Tokyo | Process for the treatment of modified polymers |
JP2001515523A (en) * | 1995-06-06 | 2001-09-18 | アライドシグナル・インコーポレーテッド | Method for producing ionomer of low molecular weight acid copolymer |
US6676870B1 (en) | 1997-10-17 | 2004-01-13 | Chisso Corporation | Process for the preparation of fiber-filled thermoplastic resin composition |
IT1298584B1 (en) | 1998-02-10 | 2000-01-12 | Montell North America Inc | EXPANDED IONOMERIC CRYSTALLINE POLYOLEFINS |
WO2000000351A1 (en) * | 1998-06-30 | 2000-01-06 | Symalit Ag | Method for producing a composite body from fibre-reinforced plastic and composite body produced according to this method |
US6280667B1 (en) | 1999-04-19 | 2001-08-28 | Andersen Corporation | Process for making thermoplastic-biofiber composite materials and articles including a poly(vinylchloride) component |
BE1012637A3 (en) * | 1999-04-29 | 2001-01-09 | Solvay | Polyolefins and method of making. |
GB0026507D0 (en) | 2000-10-30 | 2000-12-13 | Univ Leeds | Adhesive |
GB0102228D0 (en) | 2001-01-29 | 2001-03-14 | Gluco Ltd | Adhesive |
US8058354B2 (en) * | 2001-02-09 | 2011-11-15 | Eastman Chemical Company | Modified carboxylated polyolefins and their use as adhesion promoters |
US6764601B1 (en) * | 2001-04-16 | 2004-07-20 | Selecto Scientific, Inc. | Method for granulating powders |
JP4276082B2 (en) * | 2002-02-22 | 2009-06-10 | ダウ グローバル テクノロジーズ インコーポレーテッド | Macrocellular soundproof foam containing particulate additives |
EP1487561B1 (en) * | 2002-03-23 | 2010-07-21 | Omnipure Filter Company | Filtration media comprising granules of binder-agglomerated active component |
US20050221089A1 (en) * | 2002-03-23 | 2005-10-06 | Reid Roger P | Filtration media comprising granules of binder-agglomerated active component |
US7064163B2 (en) * | 2002-09-04 | 2006-06-20 | Msi Technology Llc | Polyolefin-based adhesive resins and method of making adhesive resins |
US6855771B2 (en) * | 2002-10-31 | 2005-02-15 | Grant Doney | Process for making block polymers or copolymers from isotactic polypropylene |
US6887940B2 (en) * | 2002-11-27 | 2005-05-03 | Basell Poliolefine Italia S.P.A. | Compatibilizing agent for engineering thermoplastic/polyolefin blend |
KR100816411B1 (en) * | 2003-02-14 | 2008-03-26 | 자이단호진 야마가타 다이가쿠 산교 겐큐쇼 | Polymer composite material and process for producing the same |
USRE44893E1 (en) | 2004-03-26 | 2014-05-13 | Hanwha Azdel, Inc. | Fiber reinforced thermoplastic sheets with surface coverings |
US20060069209A1 (en) * | 2004-09-29 | 2006-03-30 | Klosiewicz Daniel W | Heat stable functionalized polyolefin emulsions |
US8058355B2 (en) * | 2004-10-06 | 2011-11-15 | Eastman Chemical Company | Modified chlorinated carboxylated polyolefins and their use as adhesion promoters |
EP2074156B1 (en) | 2006-10-11 | 2013-11-06 | Universidad De Chile | Compatibilizers for producing nanocomposites, microcomposites and polymer blends and process for obtaining them. |
WO2008043750A1 (en) * | 2006-10-11 | 2008-04-17 | Universidad De Chile | Hybrid clays for obtaining nanocomposites and the preparation process of these clays and polyolefin / clay nanocomposites |
US20120220730A1 (en) * | 2011-02-24 | 2012-08-30 | Fina Technology, Inc. | High Melt Strength Polypropylene and Methods of Making Same |
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US3742093A (en) * | 1970-04-08 | 1973-06-26 | Welding Engineers | Method of separating an insoluble liquid from polymer composition |
DE2244684B2 (en) * | 1971-09-14 | 1978-02-09 | Sumitomo Chemical Co, Ltd, Osaka (Japan) | PROCESS FOR MANUFACTURING MODIFIED POLYOLEFINS |
DE2455594A1 (en) * | 1974-11-23 | 1976-05-26 | Basf Ag | PROCESS FOR PREPARING Graft Polymers |
JPS5499193A (en) * | 1978-01-23 | 1979-08-04 | Mitsubishi Petrochem Co Ltd | Preparation of modified polyolefin having improved adhesiveness |
US4283525A (en) * | 1980-02-19 | 1981-08-11 | National Starch And Chemical Corporation | Continuous process for increasing discrete particle size of solution carboxyl polymers |
JPS5856579B2 (en) * | 1980-10-09 | 1983-12-15 | 株式会社トクヤマ | Method for producing modified polypropylene composition |
JPS5836014B2 (en) * | 1980-10-09 | 1983-08-06 | 株式会社トクヤマ | Method for producing modified polypropylene composition |
US4695608A (en) * | 1984-03-29 | 1987-09-22 | Minnesota Mining And Manufacturing Company | Continuous process for making polymers having pendant azlactone or macromolecular moieties |
JPS61266411A (en) * | 1985-05-20 | 1986-11-26 | Mitsubishi Petrochem Co Ltd | Purification of maleic anhydride-modified polyolefin |
-
1988
- 1988-11-23 GB GB888827335A patent/GB8827335D0/en active Pending
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1989
- 1989-11-17 US US07/437,801 patent/US5137975A/en not_active Expired - Fee Related
- 1989-11-20 DE DE89312020T patent/DE68907320T2/en not_active Expired - Fee Related
- 1989-11-20 EP EP89312020A patent/EP0370736B1/en not_active Expired - Lifetime
- 1989-11-22 CA CA002003614A patent/CA2003614C/en not_active Expired - Fee Related
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DE68907320T2 (en) | 1993-12-23 |
EP0370736A3 (en) | 1990-08-22 |
CA2003614A1 (en) | 1990-05-23 |
DE68907320D1 (en) | 1993-07-29 |
EP0370736A2 (en) | 1990-05-30 |
GB8827335D0 (en) | 1988-12-29 |
EP0370736B1 (en) | 1993-06-23 |
US5137975A (en) | 1992-08-11 |
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